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1.
Br J Nutr ; 130(1): 33-41, 2023 07 14.
Artigo em Inglês | MEDLINE | ID: mdl-36210537

RESUMO

Duyun compound green tea (DCGT) is a healthy beverage with lipid-lowering effect commonly consumed by local people, but its mechanism is not very clear. We evaluated the effect of DCGT treatment on bile acids (BA) metabolism of mice with high-fat diet (HFD) - induced hyperlipidaemia by biochemical indexes and metabolomics and preliminarily determined the potential biomarkers and metabolic pathways of hyperlipidaemia mice treated with DCGT as well as investigated its lipid-lowering mechanism. The results showed that DCGT treatment could reduce HFD - induced gain in weight and improve dyslipidaemia. In addition, a total of ten types of BA were detected, of which seven changed BA metabolites were observed in HFD group mice. After DCGT treatment, glycocholic acid, tauroursodeoxycholic acid and taurochenodeoxycholic acid were significantly down-regulated, while hyodeoxycholic acid, deoxycholic acid and chenodeoxycholic acid were markedly up-regulated. These results demonstrated that DCGT treatment was able to make the BA metabolites in the liver of hyperlipidaemia mice normal and alleviate hyperlipidaemia by regulating the metabolites such as glycocholic acid, tauroursodeoxycholic acid and taurochenodeoxycholic, as well as the BA metabolic pathway and cholesterol metabolic pathway involved.


Assuntos
Hiperlipidemias , Doenças Metabólicas , Camundongos , Animais , Dieta Hiperlipídica/efeitos adversos , Ácido Tauroquenodesoxicólico/farmacologia , Ácido Tauroquenodesoxicólico/metabolismo , Fígado/metabolismo , Colesterol/metabolismo , Chá/química , Hiperlipidemias/tratamento farmacológico , Hiperlipidemias/etiologia , Hiperlipidemias/metabolismo , Extratos Vegetais/farmacologia , Extratos Vegetais/metabolismo , Ácido Glicocólico/metabolismo , Ácidos e Sais Biliares/metabolismo , Metabolismo dos Lipídeos , Camundongos Endogâmicos C57BL
2.
Plant Dis ; 2023 Jan 23.
Artigo em Inglês | MEDLINE | ID: mdl-36691270

RESUMO

Loquat (Rhaphiolepis biabas, heterotypic synonym: Eriobotrya japonica) is an important edible and medicinal plant that is widely cultivated on 133 thousand hectares (recorded in 2022) in China. A stem brown rot was observed on young and old trees in Mengzi city (23°23' N; 103°23' E), Yunnan Province, southwest China, during October 2014 and September 2021. Incidence ranged from 20% of trees in surrounding plantations to 50% incidence of a 160 tree orchard that was the focal point of the disease survey. Circular brown lesions occurred initially on the stems and gradually covered all the epidermis of the stem, leading to irregular dents within the bark that developed a dark brown powdery appearance (Fig.1A). Larger lesions affected vascular tissues, causing diseased trees to wither and die. Diseased tissues were surface-disinfected in a 5% sodium hypochlorite solution for 3 min, rinsed three times with sterile distilled water, placed on potato dextrose agar (PDA), and incubated in the dark at 28°C. Twenty samples were collected for tissue isolation, and 11 isolates were single-spored on water agar. In culture, the colonies on PDA were white to dark-gray, velvet, with dense hyphae, diameter 7.64 cm after 5 days. After 18 days, spherical or subglobose pycnidia were developed and semi-buried in medium, their walls were thicker and dark-brown, which were black particles surrounded by gray-black hyphae. Conidiogenous cells were hyaline, cylindrical, holoblastic, slightly swollen at the base, with rounded apex. Conidia were initially hyaline and aseptate with elliptic or ovate shape, becoming dark brown with a single septate and developing longitudinal striations along thick walls at maturity. Conidia dimensions varied from 8.0 to 12.2 × 3.8 to 6.1µm (n=50) (Fig.1D). The morphological characteristics of eleven isolates were consistent with the description of Lasiodiplodia theobromae (Alves et al. 2008). Further confirmation was also determined by sequencing the internal transcribed spacer (ITS), ß-tubulin genes, partial translation elongation factor-1α (TEF-1α) (White et al. 1990, Carbone et al. 1999, Glass et al.1995). The isolate LSB-1 was selected for DNA sequence analysis. Based on BLASTn analysis, ITS sequences (OM617921) had 98.3% similarity with L. theobromae CBS164.96 (accession AY640255), CBS124.13(accession DQ458890), CAA006 (accession DQ458891) and CBS111530 (accession EF622074), ß-tubulin sequences (OM643838) showed 99.1% similarity with L. theobromae accessions EU673110. The TEF-1α (OM643839) had 99.0% identity with L. theobromae accession EF633054. The isolate LSB-1 clustered on the same clade with other L. theobromae. Pathogenicity testing of isolate LSB-1, LSB-2, LSB-3 was conducted by inoculating the stems of l-year-old seedlings growing in pots. The epidermis at the inoculation site, 15-20 cm below the crown, was wiped with 75% alcohol cotton ball, washed three times with sterile water, and then punctured (5mm diameter) with sterile inoculation needle. A 5mm block of each isolate cultured on PDA for seven days was attached to the inoculation site. Controls were inoculated with sterile PDA blocks. The inoculation area was covered with polyethylene cling film. All inoculated seedlings were kept in controlled greenhouse at 27°C with 80% relative humidity under natural daylight conditions, and watered weekly. Each treatment was repeated three times. Eight days after inoculation, all diseased plants showed dark brown discoloration at the point of inoculation (Fig. 1G) with the bark at the inoculation site gradually raising as the disease progressed. Thirty days after inoculation, all inoculated seedlings produced typical symptoms, whereas the control seedlings remained healthy. Fungal isolates were only recovered from symptomatic stems and were morphologically identical to L. theobromae, completing Koch's postulates. According to the relevant literature, Lasiodiplodia theobromae has a broad host range, causing numerous diseases, including canker and dieback of branch (Aguilera-Cogley et al., 2021), panicle blight (Mahadevakumar et al, 2022), root rot (Abd-El Ghani and Fatouh, 2005), fruit rot(Freire et al., 2011) in diverse geographical regions. To our knowledge, this is the first report of L. theobromae causing stem brown rot of loquat in China and provides a foundation for further study of the epidemiology and integrated management of this disease.

3.
BMC Surg ; 23(1): 323, 2023 Oct 24.
Artigo em Inglês | MEDLINE | ID: mdl-37875843

RESUMO

PURPOSE: With increasing life expectancy, the number of elderly patients (≥ 65 years) with hepatocellular carcinoma (HCC) has steadily increased. Hepatectomy remains the first-line treatment for HCC patients. However, the prognosis of hepatectomy for elderly patients with HCC remains unclear. METHODS: Clinical and follow-up data from 1331 HCC patients who underwent surgery between 2008 and 2020 were retrospectively retrieved from a multicentre database. Patients were divided into elderly (≥ 65 years) and non-elderly (< 65 years) groups, and PSM was used to balance differences in the baseline characteristics. The postoperative major morbidity and cancer-specific survival (CSS) of the two groups were compared and the independent factors that were associated with the two study endpoints were identified by multivariable regression analysis. RESULTS: Of the 1331 HCC patients enrolled in this study, 363 (27.27%) were elderly, while 968 (72.73%) were not. After PSM, 334 matched samples were obtained. In the propensity score matching (PSM) cohort, a higher rate of major morbidity was found in elderly patients (P = 0.040) but the CSS was similar in the two groups (P = 0.087). Multivariate analysis revealed that elderly age was not an independent risk factor associated with high rates of major morbidity (P = 0.117) or poor CSS (P = 0.873). The 1-, 3- and 5-year CSS rates in the elderly and non-elderly groups were 91.0% versus 86.2%, 71.3% versus 68.8% and 55.9% versus 58.0%, respectively. Preoperative alpha fetoprotein (AFP) level, Child‒Pugh grade, intraoperative blood transfusion, extended hemi hepatectomy, and tumour diameter could affect the postoperative major morbidity and preoperative AFP level, cirrhosis, Child‒Pugh grade, macrovascular invasion, microvascular invasion (MVI), satellite nodules, and tumor diameter were independently and significantly associated with CSS. CONCLUSION: Age itself had no significant effect on the prognosis of elderly patients with HCC after hepatectomy. Hepatectomy can be safely performed in elderly patients after cautious perioperative management.


Assuntos
Carcinoma Hepatocelular , Neoplasias Hepáticas , Humanos , Idoso , Pessoa de Meia-Idade , Carcinoma Hepatocelular/cirurgia , Carcinoma Hepatocelular/patologia , Neoplasias Hepáticas/cirurgia , Neoplasias Hepáticas/patologia , alfa-Fetoproteínas/análise , Hepatectomia , Pontuação de Propensão , Estudos Retrospectivos , Recidiva Local de Neoplasia/cirurgia , Prognóstico
4.
Chem Soc Rev ; 51(19): 8174-8200, 2022 Oct 03.
Artigo em Inglês | MEDLINE | ID: mdl-36069165

RESUMO

Increasing social sustainability triggers the persistent progress of industrial catalysis in energy transformation and chemical production. Zeolites have been demonstrated to be pivotal catalysts in chemical industries due to their moderate acidity and versatile well-defined pore structures. However, in the context of enhancing the performances of zeolite catalysts, the perspectives on the diffusion regulations within the pores and channels in the bulk phases or external surfaces of the zeolites are often overlooked. Establishing the structure-transport-reactivity relationships in heterogeneous catalysis can provide rational guidelines to design high-performance catalysts. Herein, this tutorial review attempts to systematically depict an integrated picture of molecular transport behaviors in zeolite catalysts from macroscopic to microscopic perspectives. The advances in the accurate diffusion measurements employing both macroscopic and microscopic techniques are briefly introduced. The diffusion characteristics in zeolite catalysts under working conditions (e.g., high temperature, multi-components, and reaction coupling) are then addressed. The macroscopic internal diffusion and the microscopic diffusion occurring in the micro-zones of zeolite crystals (e.g., surface diffusion, diffusion anisotropy, and confined diffusion) are reviewed and discussed in more detail. These diffusion behaviors highly impact the underlying reaction mechanism, catalytic performances, and catalyst optimization strategies. Finally, the multi-type pore systems of practical zeolite catalysts in industrial reactors and their transport behaviors are analyzed. The fully-crystalline monolithic zeolites in the absence of binders are highlighted as rising-star catalytic materials for industrial applications. The research challenges in this field and the potential future development directions are summarized.

5.
J Am Chem Soc ; 144(9): 4260-4268, 2022 Mar 09.
Artigo em Inglês | MEDLINE | ID: mdl-35192361

RESUMO

Direct propylene epoxidation with molecular oxygen is a dream reaction with 100% atom economy, but aerobic epoxidation is challenging because of the undesired over-oxidation and isomerization of epoxide products. Herein, we report the construction of uniform cobalt ions confined in faujasite zeolite, namely, Co@Y, which exhibits unprecedented catalytic performance in the aerobic epoxidation of propylene. Propylene conversion of 24.6% is achieved at propylene oxide selectivity of 57% at 773 K, giving a state-of-the-art propylene oxide production rate of 4.7 mmol/gcat/h. The catalytic performance of Co@Y is very stable, and no activity loss can be observed for over 200 h. Spectroscopic analyses reveal the details of molecular oxygen activation on isolated cobalt ions, followed by interaction with propylene to produce epoxide, in which the Co2+-Coδ+-Co2+ (2 < δ < 3) redox cycle is involved. The reaction pathway of propylene oxide and byproduct acrolein formation from propylene epoxidation is investigated by density functional theory calculations, and the unique catalytic performance of Co@Y is interpreted. This work presents an explicit example of constructing specific transition-metal ions within the zeolite matrix toward selective catalytic oxidations.

6.
Chemistry ; 28(58): e202203088, 2022 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-36259924

RESUMO

Invited for the cover of this issue are Zaiku Xie, Jiawei Teng, Chuanming Wang, and co-workers at the SINOPEC Shanghai Research Institute of Petrochemical Technology, Liaoning Petrochemical University and University of Science and Technology of China. The image depicts the effect of eight organic additives on the anisotropic growth of classical ZSM-5 zeolite at the molecular level. Read the full text of the article at 10.1002/chem.202201781.

7.
Chemistry ; 28(58): e202201781, 2022 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-36042004

RESUMO

Zeolite morphology plays a crucial role in affecting catalytic performance, while is persistently challenging to tailor through crystal anisotropic growth. It has been recognized that specific additives can be introduced into the synthesis of zeolites to achieve anisotropic growth, however their role and the underlying mechanism are not well understood. Herein, the effect of eight specific additives on the anisotropic growth of the ZSM-5 zeolite is unveiled within the framework of crystallization engineering. Either an inhibition effect or a promotion effect is revealed for each additive according to the crystallization kinetics. The adsorption preference of typical additives on different surfaces was demonstrated by total internal reflection fluorescence microscopy (TIRFM) and transmission X-ray microscopy (TXM) together with 3D reconstruction. The calculated adsorption energy difference between MFI [100]/[101] and [010] surfaces was proposed as a key descriptor to estimate the possible morphology induced by additive. ZSM-5 zeolites varying from sphere-like, plate-like to noodle-like morphology could be synthesized by employing specific additives with increasing adsorption strength difference on distinct surfaces.

8.
Molecules ; 26(19)2021 Sep 22.
Artigo em Inglês | MEDLINE | ID: mdl-34641271

RESUMO

Boiling, the most frequent edible way to hotpot seasoning (HS), exerts a significant impact on the aroma of HS. The present study employed, for the first time, a novel switchable system between GC-O-MS and GC×GC-O-MS (SGC/GC×GC-O-MS) to study the aroma compounds of HS and hotpot seasoning boiling liquid (HSBL). A total of 79 aroma compounds and 56 aroma-active compounds were identified. The aroma extract dilution analysis (AEDA) was used to analyze the differences between the key aroma-active components in the HS and HSBL. The results showed that 13 aroma-active components were significantly affected by boiling, such as D-limonene, methional, and linalool. Moreover, a total of 22 key aroma-active components were identified through the odor activity values (OAVs) calculation. Of them, (E)-2-octenal (fatty) and linalool showed a significant difference, suggesting them to be the most critical aroma-active compounds in the HSBL, and HS, respectively. Finally, the correlation between key aroma-active compounds and the sensory properties of HS and HSBL was studied. These results demonstrated that the OAVs of key aroma-active compounds could characterize the real information of samples through bidirectional orthogonal partial least squares (O2PLS). The analysis results were consistent with the sensory evaluation results.


Assuntos
Condimentos/análise , Aromatizantes/análise , Compostos Orgânicos Voláteis/análise , Monoterpenos Acíclicos/isolamento & purificação , Cromatografia Gasosa-Espectrometria de Massas , Temperatura Alta , Análise Multivariada
9.
J Am Chem Soc ; 141(25): 9920-9927, 2019 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-31149823

RESUMO

The selective hydrogenation of alkynes to alkenes is an important type of organic transformation with large-scale industrial applications. This transformation requires efficient catalysts with precise selectivity control, and palladium-based metallic catalysts are currently employed. Here we show that four-coordinated cationic nickel(II) confined in zeolite can efficiently catalyze the selective hydrogenation of acetylene to ethylene, a key process for trace acetylene removal prior to the polymerization process. Under optimized conditions, 100% acetylene conversion and an ethylene selectivity up to 97% are simultaneously achieved. This catalyst system also exhibits good stability and recyclability for potential applications. Spectroscopy investigations and density functional theory calculations reveal the heterolytic dissociation of hydrogen molecules and the importance of hydride and protons in the selective hydrogenation of acetylene to ethylene. This work provides an efficient strategy toward active and selective zeolite catalysts by utilizing the local electrostatic field within the zeolite confined space for small-molecule activation and by linking heterogeneous and homogeneous catalysis.

10.
Neural Plast ; 2016: 2473081, 2016.
Artigo em Inglês | MEDLINE | ID: mdl-26881095

RESUMO

Due to a sedentary lifestyle, more and more people are becoming obese nowadays. In addition to health-related problems, obesity can also impair cognition and motor performance. Previous results have shown that obesity mainly affects cognition and motor behaviors through altering brain functions and musculoskeletal system, respectively. Many factors, such as insulin/leptin dysregulation and inflammation, mediate the effect of obesity and cognition and motor behaviors. Substantial evidence has suggested exercise to be an effective way to improve obesity and related cognitive and motor dysfunctions. This paper aims to discuss the association of obesity with cognition and motor behaviors and its underlying mechanisms. Following this, mechanisms of exercise to improve obesity-related dysfunctions are described. Finally, implications and future research direction are raised.


Assuntos
Cognição/fisiologia , Longevidade/fisiologia , Destreza Motora/fisiologia , Plasticidade Neuronal/fisiologia , Obesidade/fisiopatologia , Humanos , Obesidade/complicações , Obesidade/psicologia , Comportamento Sedentário
11.
Angew Chem Int Ed Engl ; 54(30): 8783-6, 2015 Jul 20.
Artigo em Inglês | MEDLINE | ID: mdl-26096840

RESUMO

Experimental evidence for the presence of tert-butyl cations, which are important intermediates in acid-catalyzed heterogeneous reactions, on solid acids has still not been provided to date. By combining density functional theory (DFT) calculations with (1)H/(13)C magic-angle-spinning NMR spectroscopy, the tert-butyl cation was successfully identified on zeolite H-ZSM-5 upon conversion of isobutene by capturing this intermediate with ammonia.

12.
Extremophiles ; 18(2): 195-206, 2014 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-24374718

RESUMO

A novel haloarchaeal plasmid, pHRDV1 (13,053 bp), was isolated from the haloarchaeal isolate Halorubrum sp. T3. Molecular and bioinformatics analyses showed that this element is a double-stranded circular DNA molecule containing two putative transcripts with opposite directions. The amino acid sequences of six of the nineteen predicted open reading frames were similar to those found in haloarchaeal pleomorphic viruses, such as Halorubrum pleomorphic virus 3 and Halogeometricum pleomorphic virus 1. There was also a strong conservation in gene order between the plasmid and these viruses. All three conserved viral proteins (VPs), which are characteristic of haloarchaeal pleomorphic viruses VP3, VP4 and VP8, were found in pHRDV1. Furthermore, a typical repressor-operator system similar to haloarchaeal myovirus φCh1, was found on the genome of pHRDV1. However, no viral particles were detected in the supernatants of Halorubrum sp. T3, either in the presence or absence of mitomycin C. These results imply that plasmid pHRDV1 is a distinctive virus-like mobile genetic element that harbors some unique properties that make it different from all of the known haloarchaeal plasmids or viruses.


Assuntos
Vírus de Archaea/genética , Halorubrum/genética , Sequências Repetitivas Dispersas , Sequência de Aminoácidos , Sequência de Bases , DNA Arqueal/genética , Genes Arqueais , Dados de Sequência Molecular , Fases de Leitura Aberta , Plasmídeos
13.
Chem Commun (Camb) ; 59(4): 470-473, 2023 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-36519521

RESUMO

An efficient zeolite interface with optimized surface barriers was tailored by passivating the hydroxyl-group defects at surfaces or near pore mouths. The surface permeability of the modified zeolite was almost 90% greater than that of the pristine one, leading to remarkable improvements in C=2-3 selectivity and an anti-inactivation rate of 75% for the catalytic cracking reaction.

14.
J Bacteriol ; 194(23): 6608-9, 2012 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-23144373

RESUMO

Halorubrum sp. strain T3, harboring a virus-like element, was isolated from a sample collected from a solar saltern in Yunnan, China. Several strains of Halorubrum pleomorphic viruses were reported in this genus recently; however, the virus-host interaction in haloarchaea remains unclear. To explore this issue, here we present the genome sequence of Halorubrum sp. strain T3 (3,168,011 bp, 68.48% G+C content).


Assuntos
Vírus de Archaea/genética , DNA Arqueal/química , DNA Arqueal/genética , Genoma Arqueal , Halorubrum/genética , Análise de Sequência de DNA , Composição de Bases , China , Microbiologia Ambiental , Halorubrum/isolamento & purificação , Halorubrum/virologia , Dados de Sequência Molecular
15.
Biochem Biophys Res Commun ; 421(4): 690-5, 2012 May 18.
Artigo em Inglês | MEDLINE | ID: mdl-22542938

RESUMO

The therapeutic applications of neural stem cells (NSCs) have potential to promote recovery in many obstinate diseases in central nervous system. Regulation of certain gene expressions using siRNA may have significant influence on the fate of NSC. To achieve the optimum gene silencing effect of siRNA, non-viral vector polyethylene glycol-polyethyleneimine (PEG-PEI) was investigated in the delivery of siRNA to NSCs. The characteristics of PEG-PEI/siRNA polyplexes were detected by scanning electron microscopy (SEM). The effects of nanoparticles on cell viability were measured via CCK-8 assay. In addition, the transfection efficiency was evaluated by fluorescence microscope and flow cytometry, and real-time PCR and Western Blot were employed to detect the gene inhibition effect of siRNA delivered by PEG-PEI. The SEM micrographs showed that PEG-PEI could condense siRNA to form diffuse and spherical nanoparticles. The cytotoxicity of PEG-PEI/siRNA nanocomplexes (N/P=15) was significantly lower when compared with that of Lipofectamine 2000/siRNA (P<0.05). Moreover, the highest transfection efficiency of PEG-PEI/siRNA nanoparticles was obtained at an N/P ratio of 15, which was better than that achieved in the transfection using Lipofectamine 2000 (P<0.05). Finally, the gene knockdown effect of PEG-PEI/siRNA nanoparticles was verified at the levels of mRNA and protein. These results suggest that PEG-PEI may potentially be used as a siRNA delivery vector for neural regeneration therapy.


Assuntos
Terapia Genética/métodos , Nanopartículas/administração & dosagem , Regeneração Nervosa , Neurônios/fisiologia , RNA Interferente Pequeno/administração & dosagem , Animais , Proteínas Ligadas por GPI/genética , Técnicas de Silenciamento de Genes , Camundongos , Proteínas da Mielina/genética , Nanopartículas/química , Receptor Nogo 1 , Polietilenoglicóis/química , Polietilenoimina/análogos & derivados , Polietilenoimina/química , RNA Interferente Pequeno/química , Receptores de Superfície Celular/genética , Transfecção
16.
RSC Adv ; 12(37): 24301-24310, 2022 Aug 22.
Artigo em Inglês | MEDLINE | ID: mdl-36128535

RESUMO

This work aims to study the effect of compound green tea (CGT) on liver lipid metabolism in mice based on metabolomics of liquid chromatography-mass spectrometry (LC-MS), and preliminarily identify potential biomarkers and pathways of action by using a metabonomic network database to explore the lipid-lowering effect of CGT. In this study, forty mice were randomly divided into four groups: compound tea treatment group (DH), high-fat model control group (NK), normal control group (CK) and positive drug group (YK). After a month of different interventions, the mice were weighed and the blood lipid indexes were detected. In addition, differential liver metabolites were monitored by using LC-MS. The results showed that CGT and positive drug treatment were able to decrease body weight, liver coefficient, TC, TG and LDL levels of obese mice, while increasing HDL levels. Among the 110 compounds obtained, 54 metabolites were significantly altered in the four comparisons. More importantly, 15 remarkably downregulated metabolites involved in Lysopc 16:1, Lysopc 18:1, and Lysopc 18:2 were found in the DH group when the mice were treated with CGT; meanwhile, the positive drug Xuezhikang was able to significantly downregulate 14 compounds, including (±)18-HEPE, and 6 keto-PGF1α, compared with the NK group. Besides, KEGG enrichment analysis also revealed the important metabolic pathways, such as linoleic acid metabolism, Biosynthesis of unsaturated fatty acids, and α-linolenic acid metabolism, were related to fatty acid metabolism. These results suggested that CGT could regulate the lipid metabolism in the liver of hyperlipidemia mice, and may regulate 54 potential biomarkers in mice through a related metabolic pathway to make them return to a normal state and improve the disorder of lipid metabolism.

17.
Chemphyschem ; 12(2): 313-21, 2011 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-21275023

RESUMO

The diarylethene derivative 1,2-bis-(5'-dimesitylboryl-2'-methylthieny-3'-yl)-cyclopentene (1) containing dimesitylboryl groups is an interesting photochromic material. The dimesitylboryl groups can bind to F(-), which tunes the optical and electronic properties of the diarylethene compound. Hence, the diarylethene derivative 1 containing dimesitylboryl groups is sensitive to both light and F(-), and its photochromic properties can be tuned by a fluoride ion. Herein, we studied the substituent effect of dimesitylboron groups on the optical properties of both the closed-ring and open-ring isomers of the diarylethene molecule by DFT/TDDFT calculations and found that these methods are reliable for the determination of the lowest singlet excitation energies of diarylethene compounds. The introduction of dimesitylboron groups to the diarylethene compound can elongate its conjugation length and change the excited-state properties from π→π* transition to a charge-transfer state. This explains the modulation of photochromic properties through the introduction of dimesitylboron groups. Furthermore, the photochromic properties can be tuned through the binding of F(-) to a boron center and the excited state of the diarylethene compound is changed from a charge-transfer state to a π→π* transition. Hence, a subtle control of the photochromic spectroscopic properties was realized. In addition, the changes of electronic characteristics by the isomerization reaction of diarylethene compounds were also investigated with theoretical calculations. For the model compound 2 without dimesitylboryl groups, the closed-ring isomer has better hole- and electron-injection abilities, as well as higher charge-transport rates, than the open-ring isomer. The introduction of dimesitylboron groups to diarylethene can dramatically improve the charge-injection and -transport abilities. The closed isomer of compound 1 (1 C) has the best hole- and electron-injection abilities, whereas the charge-transport rates of the open isomer of compound 1 (1 O) are higher than those of 1 C. Importantly, 1 O is an electron-accepting and -transport material. These results show that the diarylethene compound containing dimesitylboryl groups has promising potential to be applied in optoelectronic devices and thus is worth to be further investigated.

18.
Commun Chem ; 4(1): 107, 2021 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-36697565

RESUMO

Zeolite morphology is crucial in determining their catalytic activity, selectivity and stability, but quantitative descriptors of such a morphology effect are challenging to define. Here we introduce a descriptor that accounts for the morphology effect in the catalytic performances of H-ZSM-5 zeolite for C4 olefin catalytic cracking. A series of H-ZSM-5 zeolites with similar sheet-like morphology but different c-axis lengths were synthesized. We found that the catalytic activity and stability is improved in samples with longer c-axis. Combining time-resolved in-situ FT-IR spectroscopy with molecular dynamics simulations, we show that the difference in catalytic performance can be attributed to the anisotropy of the intracrystalline diffusive propensity of the olefins in different channels. Our descriptor offers mechanistic insight for the design of highly effective zeolite catalysts for olefin cracking.

19.
Chem Sci ; 11(37): 10113-10118, 2020 Sep 02.
Artigo em Inglês | MEDLINE | ID: mdl-34094273

RESUMO

While the [TO4] tetrahedron packing rule leads to millions of likely zeolite structures, there are currently only 252 types of zeolite frameworks reported after decades of synthetic efforts. The subtle synthetic conditions, e.g. the structure-directing agents, pH and the feed ratio, were often blamed for the limited zeolite types due to the complex kinetics. Here by developing machine learning global optimization techniques, we are now able to establish the global potential energy surface of a typical zeolite system, Si x Al y P z O2H y-z with 12 T atoms (T: Si, Al and P) that is the general formula shared by CHA, ATS, ATO and ATV zeolite frameworks. After analyzing more than 106 minima data, we identify thermodynamic rules on energetics and local bonding patterns for stable zeolites. These rules provide general guidelines to classify zeolite types and correlate them with synthesis conditions. The machine learning based atomistic simulation thus paves a new way towards rational design and synthesis of stable zeolite frameworks with desirable compositions.

20.
Front Plant Sci ; 11: 83, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32133020

RESUMO

Delayed greening of young leaves is a ubiquitous and visually striking phenomenon in the tropics. Here, we investigated the potential ecological functions of red coloration patterns in young leaves. To detect any protective function of the red coloration on the young leaves, leaf damage by insect herbivores was recorded in the field. To determine capacity for chemical defense, the concentrations of tannins and anthocyanins were measured in both young and mature leaves. To test the hypothesis that anthocyanins function as photo-protective molecules, chlorophyll content, maximum photochemical efficiency of PSII (F v /Fm ), non-photochemical quenching (NPQ), and effective quantum yield of PSII (ΦPSII ) were measured in the field. Phylogenetic relationships were analyzed to test the relationary significance of the occurrence of redness in young leaves. Compared to the coloration in non-red leaves, young red leaves had significant higher anthocyanins and tannins content and lower herbivore damages. Young, red leaves had the lowest Fv /Fm values, which were significantly lower than those of non-red leaves. NPQ values in young red leaves were comparable to those of other groups. Although young red leaves had high ΦPSII , these values were significantly lower than those of the other three groups. The results suggest that the red coloration of young leaves protects them from insect herbivory primary by chemical defense through high concentrations of tannins and anthocyanins. Additionally, low Fv /Fm values in young red leaves indicate that anthocyanins might not be functioning as light attenuators to compensate for insufficient photo-protection mediated by NPQ. And finally, red coloration in young leaves is predominantly a result of adaptation to heavy herbivory stress but without significant intrinsic phylogenetic relationship of plant species.

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